EP3681841A1 - New method for storing hydrogen - Google Patents
New method for storing hydrogenInfo
- Publication number
- EP3681841A1 EP3681841A1 EP18783061.7A EP18783061A EP3681841A1 EP 3681841 A1 EP3681841 A1 EP 3681841A1 EP 18783061 A EP18783061 A EP 18783061A EP 3681841 A1 EP3681841 A1 EP 3681841A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- alkoxyamine
- hydrogen
- borane
- complexes
- pph
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims description 27
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 23
- 229910000085 borane Inorganic materials 0.000 claims description 21
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 20
- 238000003860 storage Methods 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 6
- 239000011707 mineral Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 101150003085 Pdcl gene Proteins 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 3
- 125000005262 alkoxyamine group Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 150000002443 hydroxylamines Chemical class 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005185 salting out Methods 0.000 claims 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 21
- 239000007789 gas Substances 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- NRPJNSNRIFSGCC-UHFFFAOYSA-N B.CON Chemical compound B.CON NRPJNSNRIFSGCC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011995 wilkinson's catalyst Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- KKAXNAVSOBXHTE-UHFFFAOYSA-N boranamine Chemical class NB KKAXNAVSOBXHTE-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000003840 hydrochlorides Chemical class 0.000 description 2
- XNXVOSBNFZWHBV-UHFFFAOYSA-N hydron;o-methylhydroxylamine;chloride Chemical compound Cl.CON XNXVOSBNFZWHBV-UHFFFAOYSA-N 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 229910010082 LiAlH Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- -1 borane amine Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000763 evoking effect Effects 0.000 description 1
- LNLSXDSWJBUPHM-UHFFFAOYSA-N iminoborane Chemical class N=B LNLSXDSWJBUPHM-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- ZBDXGNXNXXPKJI-UHFFFAOYSA-N o-tert-butylhydroxylamine;hydrochloride Chemical compound Cl.CC(C)(C)ON ZBDXGNXNXXPKJI-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
- C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
- C01B6/10—Monoborane; Diborane; Addition complexes thereof
- C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
- C07C239/08—Hydroxylamino compounds or their ethers or esters
- C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/027—Organoboranes and organoborohydrides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Definitions
- the present invention relates to a novel process for storing hydrogen using alkoxyamine-borane complexes.
- alkoxyamine-borane complexes shown below have a dative bond between the nitrogen atom and BH 3 as well as amine-borane complexes.
- Physical storage is currently the most advanced technology and consists of a liquid hydrogen tank operating between 350 and 700 bar, with operating temperatures of around -120 ° C.
- Storage in the form of materials can be divided into three distinct classes: absorbent materials (zeolites, aerogels, etc.), metal hydrides (LiAlH 4 , NaBH 4 , MgH 2 , etc.) and chemical storage, in particular in the form of conventional borane amine complexes (NH 3 BH 3 , MeNH 2 BH 3 , Me 2 NHBH 3 , ).
- absorbent materials zeolites, aerogels, etc.
- metal hydrides LiAlH 4 , NaBH 4 , MgH 2 , etc.
- chemical storage in particular in the form of conventional borane amine complexes (NH 3 BH 3 , MeNH 2 BH 3 , Me 2 NHBH 3 , ).
- One of the more general aspects of the invention relates to a new simple process for storing and releasing hydrogen, not involving toxic compounds, and allowing a high hydrogen storage rate because of the low molecular weight of alkoxyamine-borane complexes.
- the present invention relates to the use of alkoxyamine-borane complexes for the storage of hydrogen.
- alkoxyamine-borane complex is intended to mean a complex formed by reaction between an alkoxyamine and a borane.
- hydrogen storage is meant, in the sense of the invention, a method for storing hydrogen and then releasing it for use.
- the present invention also relates to the use of alkoxyamine-borane complexes for the storage of hydrogen followed by a step of hydrogen release.
- hydrogen release the chemical step to obtain a release of hydrogen.
- the invention makes it possible to have a very promising chemical hydrogen reservoir.
- these compounds have a particular availability of 6.67% hydrogen mass, which is as good or better than all other types of storage.
- the present invention also relates to the use of alkoxyamine-borane complexes for the storage of hydrogen, said alkoxyamine-borane complexes being of formula (I),
- alkyl -C 10 refers to an acyclic carbon chain, saturated, linear or branched, comprising 1 to 10 carbon atoms.
- Examples of C 1 -C 10 alkyls include methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl groups.
- the definition of propyl, butyl, pentyl, hexyl or heptyl includes all possible isomers.
- butyl includes n-butyl, iso-butyl, sec-butyl and tert-butyl and the term propyl includes n-propyl and iso-propyl.
- C 3 -C 10 cycloalkyl denotes a saturated or partially saturated mono-, bi- or tri-ring comprising from 3 to 10 carbon atoms.
- the cycloalkyl group may be a cyclohexyl group.
- the present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes.
- the present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes, comprising a step of contacting at least one alkoxyamine-borane complex with a catalyst or a step of thermal heating of the above-mentioned alkoxyamine-alkane complexes. borane.
- the invention relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenating said alkoxyamine-borane complexes, and a step of contacting at least one alkoxyamine complex -borane with a catalyst of rhodium, platinum, palladium, gold or nickel, in particular selected from RhCl (PPh 3 ) 3 , NiCl 2 (PPh 3 ) 2 , Rh @ TBAB and Ni @ TBAB, Pd (OH ) 2 / C, PtCl 2 , PdCl 2 , KAuC, Pt (PPh 3 ) 4 .
- a catalyst of rhodium, platinum, palladium, gold or nickel in particular selected from RhCl (PPh 3 ) 3 , NiCl 2 (PPh 3 ) 2 , Rh @ TBAB and Ni @ TBAB, Pd (OH ) 2 / C, PtCl 2 , PdC
- the present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes, and a step of bringing an alkoxyamine-borane complex into contact with RhCl (PPh 3 ) 3 .
- the present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes, and a step of contacting an alkoxyamine-borane complex with NiCl 2 (PPli 3) 2 .
- the present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes, and a step of contacting an alkoxyamine-borane complex with Rh @ TBAB.
- the present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes, and a step of bringing an alkoxyamine-borane complex into contact with Ni @ TBAB.
- the hydrogen release reaction is generally carried out in the presence of a catalyst derived from a metal chosen from rhodium, nickel, palladium, platinum and copper, at a temperature ranging from 30 ° C. to 80 ° C. C, for a duration ranging from 3 to 1500 minutes.
- a catalyst derived from a metal chosen from rhodium, nickel, palladium, platinum and copper at a temperature ranging from 30 ° C. to 80 ° C. C, for a duration ranging from 3 to 1500 minutes.
- the hydrogen release reaction from 0.5 mmol of one of the alkoxyamine-borane complexes evoked makes it possible to produce from 5 cm 3 to 25 cm 3 of gas.
- the invention relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenating said alkoxyamine-borane complexes by thermal heating of said alkoxyamine-borane complexes above 80 ° C, preferably above 100 ° C and more preferably above 120 ° C.
- the following five alkoxyamine-borane complexes are synthesized and used in the invention.
- the present invention also relates to a process for the preparation of alkoxyamine-borane complexes of formula (I) comprising a step of placing hydroxy lamines of formula (II) in the presence of
- R and R ' are chosen from hydrogen, a C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl group, or a salt thereof, for example a hydrochloride, with NaBH 4 and a mineral acid, preferentially H 2 SO 4 or HCl, this process not requiring a purification step.
- mineral acid means an acid derived from a mineral or inorganic body, for example hydrochloric, sulfuric or nitric acid.
- the preparation of the alkoxyamine-borane complexes of formula (I) is generally carried out in an organic solvent, preferably THF (tetrahydrofuran).
- organic solvent preferably THF (tetrahydrofuran).
- the invention relates to a process for preparing the following alkoxyamine-borane complexes:
- alkoxyamine-borane complexes of formula (I) is generally carried out with a hydroxylamine / NaBH 4 hydrochloride ratio ranging from 1: 1 to 1: 2, this ratio being, according to a preferred embodiment of the invention set at 1: 1.2.
- Figure 1 relates to the study of the dehydrogenation rate of the complex (5) in the presence of 5 mol% of Wilkinson catalyst with the abscissa time expressed in minutes and the ordinate the change in the volume of gas expressed in cm 3 .
- Figure 2 relates to the study of the rate of dehydrogenation of the complex (2) in the presence of 5 mol% of Wilkinson catalyst with the abscissa time expressed in minutes and the ordinate the evolution of the volume of gas expressed in cm 3 .
- FIG. 3 relates to the study of the rate of dehydrogenation of the complex (5) in the presence of 5 mol% of NiCl 2 (PPh 3 ) 2 with the abscissa the time expressed in minutes and the ordinate the evolution of the volume of gas expressed in cm 3 .
- FIG. 4 relates to the study of the rate of dehydrogenation of the complex (5) in the presence of 5 mol% of Pt (PPh 3 ) 4 with the abscissa the time expressed in minutes and the ordinate the evolution of the volume of gas expressed in cm 3 .
- the alkoxyamine-borane complex (2) was synthesized under the same conditions as above, using O-tert-butylhydroxylamine hydrochloride, in the presence of sodium borohydride in THF (Table 2). This synthesis was first done on a small scale (CF39), then on a larger scale (CF452).
- the last alkoxyamine-borane complex synthesized is O-methylhydroxylamine borane (5) from commercial O-methylhydroxylamine hydrochloride in the presence of NaBH 4 in THF. Unlike other starting materials, this hydrochloride has low solubility in most solvents. For this synthesis, a great deal of optimization of the conditions was therefore carried out in order to improve the solubility of O-methylhydroxylamine hydrochloride (Table 5).
- alkoxyamine-borane complexes show a high potential for hydrogen storage applications because of their high hydrogen density.
- RhCl (PPh 3 ) 3 (2.5 mol%) 50 15 10
- the complexes (1), (2) and (5) have different dehydrogenation rates, the use of one or the other of these complexes thus makes it possible to modulate this rate of dehydrogenation.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Hydrogen, Water And Hydrids (AREA)
Abstract
The invention relates to the use of alkoxy-amine-borane complexes for storing hydrogen.
Description
Nouveau procédé de stockage de l'hydrogène New hydrogen storage process
La présente invention concerne un nouveau procédé de stockage de l'hydrogène utilisant des complexes alkoxyamine-boranes. The present invention relates to a novel process for storing hydrogen using alkoxyamine-borane complexes.
Les complexes alkoxyamine-boranes représentés ci-dessous comportent une liaison dative entre l'atome d'azote et BH3 tout comme les complexes amine-boranes. The alkoxyamine-borane complexes shown below have a dative bond between the nitrogen atom and BH 3 as well as amine-borane complexes.
Ces composés ne sont décrits que dans deux articles datant de 1958 (Parry et al. JACS 1958, 80, 1549 ; Parry et al. JACS 1958, 80, 1868). These compounds are described only in two articles dating back to 1958 (Parry et al., JACS 1958, 80, 1549, Parry et al., JACS 1958, 80, 1868).
/( .R' / (.R '
R NH R NH
♦ R, R' = H, alkyl ♦ R, R '= H, alkyl
BH3 BH 3
Structure générale des complexes alkoxyamine-boranes General structure of alkoxyamine-borane complexes
La synthèse de ces composés étant décrite avec des composés toxiques et qui ne sont plus utilisés tels que le diborane gaz, il était donc nécessaire de mettre au point une synthèse peu ou pas toxique, économique et permettant une montée en échelle aisée. The synthesis of these compounds being described with toxic compounds and which are no longer used such as diborane gas, it was therefore necessary to develop a low or no toxic synthesis, economic and easy scaling up.
Les solutions actuelles pour le stockage de l'hydrogène se décomposent en deux grandes familles : le stockage physique et le stockage sous forme de matériaux. Current solutions for hydrogen storage break down into two main families: physical storage and material storage.
Le stockage physique est actuellement la technologie la plus aboutie et consiste en un réservoir d'hydrogène liquide fonctionnant entre 350 et 700 bar, avec des températures de fonctionnement de l'ordre de -120°C. Physical storage is currently the most advanced technology and consists of a liquid hydrogen tank operating between 350 and 700 bar, with operating temperatures of around -120 ° C.
Le stockage sous forme de matériaux peut être divisé en trois classes distinctes : les matériaux absorbants (zéolites, aérogels, ...), les hydrures métalliques (LiAlH4, NaBH4, MgH2, ...) et le stockage chimique, notamment sous forme de complexes aminé borane classiques (NH3BH3, MeNH2BH3, Me2NHBH3, ...). Storage in the form of materials can be divided into three distinct classes: absorbent materials (zeolites, aerogels, etc.), metal hydrides (LiAlH 4 , NaBH 4 , MgH 2 , etc.) and chemical storage, in particular in the form of conventional borane amine complexes (NH 3 BH 3 , MeNH 2 BH 3 , Me 2 NHBH 3 , ...).
Les solutions précédemment citées présentent néanmoins des inconvénients : les conditions drastiques de température et de pression pour le stockage physique, le coût et l'encrassement des matériaux pour les matériaux absorbants, la nécessité d'employer des réactifs en condition
stœchiométrique pour avoir une déshydrogénation réversible des hydrures de métaux, et enfin une réhydrogénation compliquée des complexes amine-borane classiques. The aforementioned solutions nevertheless have disadvantages: the drastic temperature and pressure conditions for the physical storage, the cost and the fouling of the materials for the absorbent materials, the need to use reagents in condition stoichiometric to have a reversible dehydrogenation of metal hydrides, and finally a complicated rehydrogenation of conventional amine-borane complexes.
La transformation des complexes alkoxyamine-boranes par déshydrogénation catalytique aminoboranes et iminoboranes correspondants n'a jamais été décrite. The transformation of alkoxyamine-borane complexes by catalytic dehydrogenation of corresponding aminoboranes and iminoboranes has never been described.
L'un des aspects les plus généraux de l'invention concerne un nouveau procédé simple de stockage et de relargage de l'hydrogène, n'impliquant pas de composés toxiques, et permettant un fort taux de stockage de l'hydrogène en raison du faible poids moléculaire des complexes alkoxyamine-boranes. One of the more general aspects of the invention relates to a new simple process for storing and releasing hydrogen, not involving toxic compounds, and allowing a high hydrogen storage rate because of the low molecular weight of alkoxyamine-borane complexes.
Selon l'un de ses aspects les plus généraux, la présente invention concerne l'utilisation de complexes alkoxyamine-boranes pour le stockage de l'hydrogène. According to one of its more general aspects, the present invention relates to the use of alkoxyamine-borane complexes for the storage of hydrogen.
Au sens de l'invention, il est entendu par «complexe alkoxyamine-borane », un complexe formé par réaction entre une alkoxyamine et un borane. For the purposes of the invention, the term "alkoxyamine-borane complex" is intended to mean a complex formed by reaction between an alkoxyamine and a borane.
Par « stockage d'hydrogène », il est entendu, au sens de l'invention, une méthode permettant de conserver de l'hydrogène pour ensuite le libérer en vue de son utilisation. By "hydrogen storage" is meant, in the sense of the invention, a method for storing hydrogen and then releasing it for use.
La présente invention concerne également l'utilisation de complexes alkoxyamine-boranes pour le stockage de l'hydrogène suivi d'une étape de relargage de l'hydrogène. The present invention also relates to the use of alkoxyamine-borane complexes for the storage of hydrogen followed by a step of hydrogen release.
Au sens de l'invention, il est entendu par «relargage d'hydrogène », l'étape chimique permettant d'obtenir un dégagement d'hydrogène. For the purposes of the invention, it is understood by "hydrogen release", the chemical step to obtain a release of hydrogen.
L'invention permet de disposer d'un réservoir chimique d'hydrogène très prometteur. Ainsi, ces composés présentent une disponibilité notamment de 6,67% d'hydrogène en masse, ce qui est aussi bon, voire meilleur que tous les autres types de stockage. The invention makes it possible to have a very promising chemical hydrogen reservoir. Thus, these compounds have a particular availability of 6.67% hydrogen mass, which is as good or better than all other types of storage.
La présente invention concerne également l'utilisation de complexes alkoxyamine-boranes pour le stockage de l'hydrogène, lesdits complexes alkoxyamine-boranes étant de formule (I), The present invention also relates to the use of alkoxyamine-borane complexes for the storage of hydrogen, said alkoxyamine-borane complexes being of formula (I),
R NH (i) R NH (i)
BH3 BH 3
pour laquelle R et R' sont choisis indépendamment parmi un hydrogène, un groupement alkyle en Ci à Cio ou cycloalkyle en C3 à Cio.
Au sens de l'invention, l'expression « alkyle en Ci à C10 » désigne une chaîne carbonée acyclique, saturée, linéaire ou ramifiée, comprenant 1 à 10 atomes de carbone. Des exemples d'alkyles en Ci à C10 incluent les groupes méthyle, éthyle, propyle, butyle, pentyle, hexyle ou heptyle. La définition de propyle, butyle, pentyle, hexyle ou heptyle inclut tous les isomères possibles. Par exemple, le terme butyle comprend n-butyle, iso-butyle, sec-butyle et tert- butyle et le terme propyle comprend n-propyle et iso -propyle. wherein R and R 'are independently selected from hydrogen, alkyl Ci-Cio cycloalkyl or C 3 -C. Within the meaning of the invention, the term "alkyl -C 10" refers to an acyclic carbon chain, saturated, linear or branched, comprising 1 to 10 carbon atoms. Examples of C 1 -C 10 alkyls include methyl, ethyl, propyl, butyl, pentyl, hexyl or heptyl groups. The definition of propyl, butyl, pentyl, hexyl or heptyl includes all possible isomers. For example, the term butyl includes n-butyl, iso-butyl, sec-butyl and tert-butyl and the term propyl includes n-propyl and iso-propyl.
Au sens de la présente invention, l'expression «cycloalkyle en C3 à C10 » désigne un mono-, bi- ou tri-cycle saturé ou partiellement saturé, comprenant de 3 à 10 atomes de carbone. Par exemple, le groupement cycloalkyle peut être un groupement cyclohexyle. For the purposes of the present invention, the expression "C 3 -C 10 cycloalkyl" denotes a saturated or partially saturated mono-, bi- or tri-ring comprising from 3 to 10 carbon atoms. For example, the cycloalkyl group may be a cyclohexyl group.
La présente invention concerne également un procédé de relargage d'hydrogène à partir de complexes alkoxyamine-boranes comprenant une étape de déshydrogénation desdits complexes alkoxyamine-boranes. La présente invention concerne également un procédé de relargage d'hydrogène à partir de complexes alkoxyamine-boranes, comprenant une étape de mise en contact d'au moins un complexe alkoxyamine-borane avec un catalyseur ou une étape de chauffage thermique des susdits complexes alkoxyamine-boranes. Selon un mode de réalisation avantageux, l'invention concerne un procédé de relargage d'hydrogène à partir de complexes alkoxyamine-boranes comprenant une étape de déshydrogénation desdits complexes alkoxyamine-boranes, et une étape de mise en contact d'au moins un complexe alkoxyamine-borane avec un catalyseur de rhodium, de platine, de palladium, d'or ou de nickel, notamment choisi parmi RhCl(PPh3)3, NiCl2(PPh3)2, Rh@TBAB et Ni@TBAB, Pd(OH)2/C, PtCl2, PdCl2, KAuC , Pt(PPh3)4. The present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes. The present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes, comprising a step of contacting at least one alkoxyamine-borane complex with a catalyst or a step of thermal heating of the above-mentioned alkoxyamine-alkane complexes. borane. According to an advantageous embodiment, the invention relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenating said alkoxyamine-borane complexes, and a step of contacting at least one alkoxyamine complex -borane with a catalyst of rhodium, platinum, palladium, gold or nickel, in particular selected from RhCl (PPh 3 ) 3 , NiCl 2 (PPh 3 ) 2 , Rh @ TBAB and Ni @ TBAB, Pd (OH ) 2 / C, PtCl 2 , PdCl 2 , KAuC, Pt (PPh 3 ) 4 .
La présente invention concerne également un procédé de relargage d'hydrogène à partir de complexes alkoxyamine-boranes comprenant une étape de déshydrogénation desdits complexes alkoxyamine-boranes, et une étape de mise en contact d'un complexe alkoxyamine-borane avec RhCl(PPh3)3. The present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes, and a step of bringing an alkoxyamine-borane complex into contact with RhCl (PPh 3 ) 3 .
La présente invention concerne également un procédé de relargage d'hydrogène à partir de complexes alkoxyamine-boranes comprenant une étape de déshydrogénationdes dits
complexes alkoxyamine-boranes, et une étape de mise en contact d'un complexe alkoxyamine-borane avec NiCl2(PPli3)2. The present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes, and a step of contacting an alkoxyamine-borane complex with NiCl 2 (PPli 3) 2 .
La présente invention concerne également un procédé de relargage d'hydrogène à partir de complexes alkoxyamine-boranes comprenant une étape de déshydrogénation desdits complexes alkoxyamine-boranes, et une étape de mise en contact d'un complexe alkoxyamine-borane avec Rh@TBAB. The present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes, and a step of contacting an alkoxyamine-borane complex with Rh @ TBAB.
La présente invention concerne également un procédé de relargage d'hydrogène à partir de complexes alkoxyamine-boranes comprenant une étape de déshydrogénation desdits complexes alkoxyamine-boranes, et une étape de mise en contact d'un complexe alkoxyamine-borane avec Ni@TBAB. The present invention also relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes, and a step of bringing an alkoxyamine-borane complex into contact with Ni @ TBAB.
La réaction de relargage d'hydrogène est en général réalisée en présence d'un catalyseur dérivé d'un métal choisi parmi le rhodium, le nickel, le palladium, le platine, le cuivre, à une température allant de 30°C à 80°C, pour une durée allant de 3 à 1500 minutes. The hydrogen release reaction is generally carried out in the presence of a catalyst derived from a metal chosen from rhodium, nickel, palladium, platinum and copper, at a temperature ranging from 30 ° C. to 80 ° C. C, for a duration ranging from 3 to 1500 minutes.
La réaction de relargage d'hydrogène à partir de 0.5 mmol d'un des complexes alkoxyamine- boranes suscités permet de produire de 5 cm3 à 25 cm3 de gaz. The hydrogen release reaction from 0.5 mmol of one of the alkoxyamine-borane complexes evoked makes it possible to produce from 5 cm 3 to 25 cm 3 of gas.
Selon un autre mode de réalisation avantageux, l'invention concerne un procédé de relargage d'hydrogène à partir de complexes alkoxyamine-boranes comprenant une étape de déshydrogénation des dits complexes alkoxyamine-boranes par chauffage thermique des susdits complexes alkoxyamine-boranes au-dessus de 80°C, préférentiellement au-dessus de 100°C et plus préférentiellement au-dessus de 120°C. According to another advantageous embodiment, the invention relates to a process for the release of hydrogen from alkoxyamine-borane complexes comprising a step of dehydrogenating said alkoxyamine-borane complexes by thermal heating of said alkoxyamine-borane complexes above 80 ° C, preferably above 100 ° C and more preferably above 120 ° C.
Selon un mode de réalisation particulier de l'invention, les cinq complexes alkoxyamine- boranes suivants sont synthétisés et utilisés dans l'invention. According to a particular embodiment of the invention, the following five alkoxyamine-borane complexes are synthesized and used in the invention.
(1 ) (2) (3) (4) (5)
La présente invention concerne également un procédé de préparation de complexes alkoxyamine-boranes de formule (I) comprenant une étape de mise en présence d'hydroxy lamines de formule (II),
(1) (2) (3) (4) (5) The present invention also relates to a process for the preparation of alkoxyamine-borane complexes of formula (I) comprising a step of placing hydroxy lamines of formula (II) in the presence of
pour laquelle R et R' sont choisis parmi un hydrogène ou un groupement alkyle en Ci à C10 ou cycloalkyle en C3 à C10, ou d'un de leurs sels, par exemple un chlorhydrate, avec NaBH4 et un acide minéral, préférentiellement H2S04 ou HCl, ce procédé ne nécessitant pas d'étape de purification. for which R and R 'are chosen from hydrogen, a C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl group, or a salt thereof, for example a hydrochloride, with NaBH 4 and a mineral acid, preferentially H 2 SO 4 or HCl, this process not requiring a purification step.
Au sens de l'invention, il est entendu par «acide minéral », un acide dérivé d'un corps minéral ou inorganique, par exemple l'acide chlorhydrique, sulfurique ou nitrique. For the purposes of the invention, the term "mineral acid" means an acid derived from a mineral or inorganic body, for example hydrochloric, sulfuric or nitric acid.
La préparation des complexes alkoxyamine-boranes de formule (I) est en général réalisée dans un solvant organique, de préférence le THF (tétrahydrofurane). The preparation of the alkoxyamine-borane complexes of formula (I) is generally carried out in an organic solvent, preferably THF (tetrahydrofuran).
Selon un mode de réalisation avantageux, l'invention concerne un procédé de préparation des complexes alkoxyamine-boranes suivants :
According to an advantageous embodiment, the invention relates to a process for preparing the following alkoxyamine-borane complexes:
(1 ) (2) (3) (4) (5) comprenant une étape de mise en présence respectivement des chlorhydrates d'hydroxy lamines suivants : (1) (2) (3) (4) (5) comprising a step of bringing into contact respectively the following hydrochloride hydroxylamine:
avec NaBH4 et un acide minéral, préférentiellement H2S04 ou HCl, ce procédé ne nécessitant pas d'étape de purification.
La préparation des complexes alkoxyamine-boranes de formule (I) est en général réalisée avec un rapport chlorhydrate d'hydroxy lamine / NaBH4 allant de 1 : 1 à 1 :2, ce rapport étant selon un mode préféré de l'invention fixé à 1 : 1.2. Légendes des figures : with NaBH 4 and a mineral acid, preferentially H 2 SO 4 or HCl, this process not requiring a purification step. The preparation of the alkoxyamine-borane complexes of formula (I) is generally carried out with a hydroxylamine / NaBH 4 hydrochloride ratio ranging from 1: 1 to 1: 2, this ratio being, according to a preferred embodiment of the invention set at 1: 1.2. Legends of figures:
La Figure 1 concerne l'étude de la vitesse de déshydrogénation du complexe (5) en présence de 5 mol% de catalyseur de Wilkinson avec en abscisses le temps exprimé en minutes et en ordonnées l'évolution du volume de gaz exprimée en cm3. Figure 1 relates to the study of the dehydrogenation rate of the complex (5) in the presence of 5 mol% of Wilkinson catalyst with the abscissa time expressed in minutes and the ordinate the change in the volume of gas expressed in cm 3 .
La Figure 2 concerne l'étude de la vitesse de déshydrogénation du complexe (2) en présence de 5 mol% de catalyseur de Wilkinson avec en abscisses le temps exprimé en minutes et en ordonnées l'évolution du volume de gaz exprimée en cm3. Figure 2 relates to the study of the rate of dehydrogenation of the complex (2) in the presence of 5 mol% of Wilkinson catalyst with the abscissa time expressed in minutes and the ordinate the evolution of the volume of gas expressed in cm 3 .
La Figure 3 concerne l'étude de la vitesse de déshydrogénation du complexe (5) en présence de 5 mol% de NiCl2(PPh3)2 avec en abscisses le temps exprimé en minutes et en ordonnées l'évolution du volume de gaz exprimée en cm3. FIG. 3 relates to the study of the rate of dehydrogenation of the complex (5) in the presence of 5 mol% of NiCl 2 (PPh 3 ) 2 with the abscissa the time expressed in minutes and the ordinate the evolution of the volume of gas expressed in cm 3 .
La Figure 4 concerne l'étude de la vitesse de déshydrogénation du complexe (5) en présence de 5 mol% de Pt(PPh3)4 avec en abscisses le temps exprimé en minutes et en ordonnées l'évolution du volume de gaz exprimée en cm3. FIG. 4 relates to the study of the rate of dehydrogenation of the complex (5) in the presence of 5 mol% of Pt (PPh 3 ) 4 with the abscissa the time expressed in minutes and the ordinate the evolution of the volume of gas expressed in cm 3 .
Exemples relatifs à la préparation des complexes alkoxyamine-boranes : Examples relating to the preparation of alkoxyamine-borane complexes:
Exemple 1 : Example 1
Les essais réalisés par les Inventeurs pour synthétiser un complexe alkoxyamine-borane à partir de la Ν,Ο-diméthylhydroxylamine uniquement en présence de NaBH4 dans le THF ont abouti à un bon rendement de 77% en 2h. The tests carried out by the inventors to synthesize an alkoxyamine-borane complex from Ν, Ο-dimethylhydroxylamine only in the presence of NaBH 4 in THF gave a good yield of 77% over 2 hours.
Θ Θ
Cl
Cl
Un travail d'optimisation mené sur cette synthèse (Tableau 1) a permis d'accéder à un rendement de 86%. Les résultats montrent que le ratio optimum entre l'alkoxyamme-HCl et NaBH4 est de 1 : 1.2. Le complexe obtenu ne nécessite pas de purification.
NaBH4 An optimization work carried out on this synthesis (Table 1) allowed to reach a yield of 86%. The results show that the optimum ratio between alkoxyam-HCl and NaBH 4 is 1: 1.2. The resulting complex does not require purification. NaBH 4
/ .HCI .0. / / .HCI .0. /
NH NH
H THF BH3 H THF BH 3
(1 ) (1)
Référence NaBH4 (éq.) Température (°C) Temps (h) Traitement Rdt (%)Reference NaBH 4 (eq.) Temperature (° C) Time (h) Treatment Yield (%)
CF32dry 2 70 72 NaHC03/DCM 6.5 CF32dry 2 70 72 NaHC0 3 / DCM 6.5
CF35 2 ta. 48 NaHC03/DCM 76 CF35 2 ta. 48 NaHCO 3 / DCM 76
CF65 1.6 ta. 24 NaHC03/DCM 64 CF65 1.6 ta. 24 NaHC0 3 / DCM 64
CF651 1.2 70 24 NaHC03/DCM 86 CF651 1.2 70 24 NaHC0 3 / DCM 86
CF673 1.2 70 24 NaHC03/DCM 63 CF673 1.2 70 24 NaHCO 3 / DCM 63
CF652 1.2 ta. 24 NaHC03/DCM 51CF652 1.2 ta. 24 NaHC0 3 / DCM 51
CF653 2 ta. 24 NaHC03/DCM 79 CF653 2 ta. 24 NaHC0 3 / DCM 79
CF6541 1.2 ta. 2 NaHC03/DCM 68 CF6541 1.2 ta. 2 NaHC0 3 / DCM 68
CF6542 1.2 ta. 2 H20/AcOEt 77 CF6542 1.2 ta. 2 H 2 0 / AcOEt 77
Tableau 1 Table 1
Exemple 2 : Example 2
Le complexe alkoxyamine-borane (2) a été synthétisé dans les mêmes conditions que ci- dessus, en utilisant le chlorhydrate de O-tertbutylhydroxylamine, en présence de borohydrure de sodium dans le THF (Tableau 2). Cette synthèse a d'abord été réalisée sur petite échelle (CF39), puis sur plus grande échelle (CF452). The alkoxyamine-borane complex (2) was synthesized under the same conditions as above, using O-tert-butylhydroxylamine hydrochloride, in the presence of sodium borohydride in THF (Table 2). This synthesis was first done on a small scale (CF39), then on a larger scale (CF452).
(2) (2)
Référence NaBH4 (éq.) Température (°C) Temps (h) Traitement Rdt (%)Reference NaBH 4 (eq.) Temperature (° C) Time (h) Treatment Yield (%)
CF39 2 ta. 24 NaHC03/DCM 38 CF39 2 ta. 24 NaHC0 3 / DCM 38
CF452 2 ta. 24 NaHC03/DCM 64 CF452 2 ta. 24 NaHC0 3 / DCM 64
CF522 1.3 ta. 24 NaHCOVDCM 48 CF522 1.3 ta. 24 NaHCOVDCM 48
Tableau 2
Exemples 3 et 4 : Table 2 Examples 3 and 4:
Au contraire des précédentes synthèses, les complexes alkoxyamine-boranes (3) et (4) ont été préparés à partir de chlorhydrates non commerciaux (Tableaux 3, 4 et 5) qui ont donc dû être préalablement synthétisés. In contrast to the previous syntheses, the alkoxyamine-borane (3) and (4) complexes were prepared from non-commercial hydrochlorides (Tables 3, 4 and 5) which therefore had to be synthesized beforehand.
(3) (3)
Référence NaBH4 (éq.) Température (°C) Temps (h) Traitement Rdt (%) Reference NaBH 4 (eq.) Temperature (° C) Time (h) Treatment Yield (%)
CF77 1.2 ta. 24 H20/Et20 37.6 CF77 1.2 ta. 24 H 2 0 / And 2 0 37.6
CF80 1.2 ta. 24 H20/Et20 35 CF80 1.2 ta. 24 H 2 0 / And 2 0 35
Tableau 3 Table 3
Référence NaBH4 (éq.) Température (°C) Temps (h) Traitement Rdt (%) Reference NaBH 4 (eq.) Temperature (° C) Time (h) Treatment Yield (%)
CF89 1.2 ta. 24 H20/Et20 65 CF89 1.2 ta. 24 H 2 0 / And 2 0 65
CF97 1.2 ta. 24 H20/Et20 18 CF97 1.2 ta. 24 H 2 0 / And 2 0 18
Tableau 4 Exemple 5 : Table 4 Example 5:
Le dernier complexe alkoxyamine-borane synthétisé est le O-méthylhydroxylamine borane (5) à partir du chlorhydrate de O-méthylhydroxylamine commercial en présence de NaBH4 dans le THF. A la différence des autres produits de départ, ce chlorhydrate présente une faible solubilité dans la majorité des solvants. Pour cette synthèse, un gros travail d'optimisation des conditions a donc été réalisé dans le but d'améliorer la solubilité du chlorhydrate de O- méthylhydroxylamine (Tableau 5).
The last alkoxyamine-borane complex synthesized is O-methylhydroxylamine borane (5) from commercial O-methylhydroxylamine hydrochloride in the presence of NaBH 4 in THF. Unlike other starting materials, this hydrochloride has low solubility in most solvents. For this synthesis, a great deal of optimization of the conditions was therefore carried out in order to improve the solubility of O-methylhydroxylamine hydrochloride (Table 5).
(5) (5)
NaBH4 Température Temps Rdt Commentaires/NaBH 4 Temperature Time Rdt Comments /
Référence Traitement Reference Treatment
(éq.) (°C) (h) (%) Modifications (eq.) (° C) (h) (%) Changes
CF44 2 t.a. 24 NaHC03/DCM 21 CF44 2 ta 24 NaHCO 3 / DCM 21
CF462 2 t.a. 24 NaHC03/DCM 10 CF462 2 ta 24 NaHCO 3 / DCM 10
CF53 1.25 t.a. 24 NaHC03/DCM 17 CF53 1.25 ta 24 NaHCO 3 / DCM 17
CF571 1.2 70 24 NaHC03/DCM 18 CF571 1.2 70 24 NaHC0 3 / DCM 18
CF645 1.2 70 24 NaHC03/DCM 7 Sonication lh CF645 1.2 70 24 NaHC0 3 / DCM 7 Sonication lh
Déshydrogénation (20 Dehydrogenation (20
CF648 1.2 t.a. 24 H20/Et20 47 CF648 1.2 ta 24 H 2 0 / And 2 O 47
mL de gaz formé) mL of formed gas)
CF64EtA 1.2 t.a. 24 H20/Et20 12 Solvant : THF/AcOEt CF64EtA 1.2 ta 24 H 2 0 / Et 2 0 12 Solvent: THF / AcOEt
Solvant : Solvent:
CF64EtA2 2 t.a. 24 H20/Et20 28 CF64EtA2 2 ta 24 H 2 0 / And 2 0 28
THF/AcOEt/EtOH THF / EtOAc / EtOH
Déshydrogénation (15Dehydrogenation (15
CF64De2 1.2 30 24 H20/Et20 43 mL des 40 mL de gaz attendu)CF64De2 1.2 30 24 H 2 0 / And 2 0 43 mL of the 40 mL of expected gas)
CF641eq 1 30 24 H20/Et20 44 CF641eq 1 30 24 H 2 0 / And 2 0 44
Difficultés à sécher le Difficulties drying the
CF642eq 2 30 24 H20/Et20 246 CF642eq 2 30 24 H 2 0 / And 2 0 246
produit product
CF64H20 1.2 30 24 H20/Et20 64 Solvant : THF/H20CF64H20 1.2 30 24 H 2 0 / Et 2 0 64 Solvent: THF / H 2 0
CF64H201 1.2 30 24 H20/Et20 53 THF en excèsCF64H201 1.2 30 24 H 2 0 / And 2 0 53 THF in excess
CF64H202 1.2 30 24 H20/Et20 46 Moins de THF CF64H202 1.2 30 24 H 2 0 / And 2 0 46 Less THF
Addition rapide d'une Quick addition of a
CF64H203 1.2 30 24 H20/Et20 17 solution MeONH3 +Cl" CF64H203 1.2 30 24 H 2 0 / And 2 0 17 MeONH solution 3 + Cl "
/H20 / H 2 0
Addition goutte à goutte Addition drip
CF64H204 1.2 30 24 H20/Et20 14 d'une solution CF64H204 1.2 30 24 H 2 0 / And 2 0 14 of a solution
MeONH3 +C17H20MeONH 3 + C17H 2 0
CF64H205 1.2 30 72 H20/Et20 20 NaBH4 ajouté en dernierCF64H205 1.2 30 72 H 2 0 / Et 2 0 20 NaBH 4 last added
CF64H206 1.2 30 24 H20/Et20 26 NaBH4 ajouté en dernier CF64H206 1.2 30 24 H 2 0 / And 2 0 26 NaBH 4 last added
Solution saturée de Saturated solution of
CF64H207 1.2 30 24 H20/Et20 44 CF64H207 1.2 30 24 H 2 0 / And 2 0 44
MeONH3 +C17H20
Solution diluée deMeONH 3 + C17H 2 0 Diluted solution of
CF64H208 1.2 30 24 H20/Et20 39 CF64H208 1.2 30 24 H 2 0 / And 2 0 39
MeONH3 +C17H20MeONH 3 + C17H 2 0
Tableau 5 Table 5
Exemples relatifs à la déshydrogénation des complexes alkoxyamine-boranes : Examples relating to the dehydrogenation of alkoxyamine-borane complexes:
De nombreuses recherches ont été menées sur les complexes alkoxyamine-boranes (1), (2) et (5). Ces expériences ont permis de mettre en lumière les propriétés intéressantes de la liaison dative bore-azote. Le but de ces expériences était ainsi d'établir l'utilité de ces composés en tant que précurseurs dans certaines réactions, par exemple dans la formation d'aminoboranes par déshydrogénation. Much research has been conducted on alkoxyamine-borane complexes (1), (2) and (5). These experiments made it possible to highlight the interesting properties of the dative boron-nitrogen bond. The purpose of these experiments was thus to establish the usefulness of these compounds as precursors in certain reactions, for example in the formation of aminoboranes by dehydrogenation.
De plus, les complexes alkoxyamine-boranes montrent un fort potentiel pour des applications de stockage de l'hydrogène en raison de leur forte densité en hydrogène. In addition, the alkoxyamine-borane complexes show a high potential for hydrogen storage applications because of their high hydrogen density.
La déshydrogénation des suscités complexes alkoxyamine-boranes en présence de catalyseurs à base de métaux de transition est ici décrite. The dehydrogenation of the alkoxyamine-borane complex complexes in the presence of transition metal catalysts is here described.
Exemple 6 : Example 6
Les catalyseurs les plus efficaces se sont révélés être le catalyseur de Wilkinson (RhCl(PPh3)3) et NiCl2(PPh3)2 avec lesquels 1 équivalent d'hydrogène a été relargué à partir de chaque complexe alkox amine-borane (Tableaux 6, 7 et 8). The most effective catalysts have been found to be the Wilkinson (RhCl (PPh 3 ) 3) and NiCl 2 (PPh 3 ) 2 catalyst with which 1 equivalent of hydrogen has been salted out from each alkoxamine-borane complex (Tables 6, 7 and 8).
HH
Catalyseur Température (°C) Temps (min) Volume de gaz formé (cm3)Catalyst Temperature (° C) Time (min) Volume of gas formed (cm 3 )
PdCl2dppp 70 40 20 PdCl 2 dppp 70 40 20
Pd(OAc)2 70 85 36 Pd (OAc) 2 70 85 36
Pd(OH)2/C 70 540 15.5 Pd (OH) 2 / C 70 540 15.5
NiCl2.6H20 70 1440 6 NiCl 2 .6H 2 0 70 1440 6
RuCl2.xH20 30 - -RuCl 2 .xH 2 0 30 - -
PtCl2 30-50 900 20 PtCl 2 30-50 900 20
RhCl(PPh3)3 30 7 22 RhCl (PPh 3 ) 3 30 7 22
NiCl2(PPh3)3 30 29 22
PdCl2 30 47 22 NiCl 2 (PPh 3 ) 3 30 29 22 PdCl 2 30 47 22
Cul 30 - -
Ass 30 - -
Pt(PPh3)4 30-70 204 14 Pt (PPh 3 ) 4 30-70 204 14
Tableau 6 Table 6
Exemples 7 et 8 : Examples 7 and 8:
Catalyseur Température (°C) Temps (min) Volume de gaz formé (cm3)Catalyst Temperature (° C) Time (min) Volume of gas formed (cm 3 )
Pd(OAc)2 30-70 - -Pd (OAc) 2 30-70 - -
Pd(OH)2/C 30-70 900 5.5 Pd (OH) 2 / C 30-70 900 5.5
PtCl2 30-70 900 8 PtCl 2 30-70 900 8
RhCl(PPh3)3 30 12 8.5 RhCl (PPh 3 ) 3 30 12 8.5
NiCl2(PPh3)3 40 11.20 10 NiCl 2 (PPh 3 ) 3 40 11.20 10
PdCl2 70 47.50 22 PdCl 2 70 47.50 22
Tableau 7 Table 7
Catalyseur Température (°C) Temps (min) Volume de gaz formé (cm3)Catalyst Temperature (° C) Time (min) Volume of gas formed (cm 3 )
Pd(OAc)2 50-80 900 9Pd (OAc) 2 50-80 900 9
Pd(OH)2/C 60-80 1050 8 Pd (OH) 2 / C 60-80 1050 8
PtCl2 (dans THF) 50 900 10 PtCl 2 (in THF) 50,900
RhCl(PPh3)3 (2.5 mol%) 50 15 10 RhCl (PPh 3 ) 3 (2.5 mol%) 50 15 10
NiCl2(PPh3)3 30-50 36 12 NiCl 2 (PPh 3 ) 3 30-50 36 12
Tableau 8
La comparaison des vitesses de décomposition des trois complexes alkoxyamine-boranes (1), (2) et (5) montre clairement que le Ν,Ο-diméthylhydroxylamine borane (1) est le moins stable des trois. Table 8 The comparison of the decomposition rates of the three alkoxyamine-borane complexes (1), (2) and (5) clearly shows that Ν, Ο-dimethylhydroxylamine borane (1) is the least stable of the three.
Les complexes (1), (2) et (5) présentent des vitesses de déshydrogénation différentes, l'utilisation de l'un ou l'autre de ces complexes permet donc de moduler cette vitesse de déshydrogénation. The complexes (1), (2) and (5) have different dehydrogenation rates, the use of one or the other of these complexes thus makes it possible to modulate this rate of dehydrogenation.
Exemple 9 : Example 9
Des essais supplémentaires ont été menés sur le complexe O-méthylhydroxylamine borane (5) avec le catalyseur de Wilkinson (RhCl(PPh3)3), NiCl2(PPh3)2 et les nanocatalyseurs correspondants à 50°C (Tableau 9). Additional tests were carried out on the O-methylhydroxylamine borane complex (5) with the Wilkinson catalyst (RhCl (PPh 3 ) 3), NiCl 2 (PPh 3 ) 2 and the corresponding nanocatalysts at 50 ° C. (Table 9).
Les deux nanocatalyseurs sont apparus comme efficaces dans la réaction de déshydrogénation du O-méthylhydroxylamine borane (5). Both nanocatalysts appeared to be effective in the dehydrogenation reaction of O-methylhydroxylamine borane (5).
Catalyseur Température (°C) Temps (min) Volume de gaz formé (cm3)Catalyst Temperature (° C) Time (min) Volume of gas formed (cm 3 )
RhCl(PPh3)3 50-80 3 10 RhCl (PPh 3 ) 3 50-80 3 10
NiCl2(PPh3)3 60-80 6 9 NiCl 2 (PPh 3 ) 3 60-80 6 9
Rh@TBAB 50 37 15 Rh @ TBAB 50 37 15
Ni@TBAB 50 900 11 Neither @ TBAB 50 900 11
RhCl(PPh3)3 RhCl (PPh 3 ) 3
60 108 15.5 60 108 15.5
(1 mol% supplémentaire) (1% additional mole)
Tableau 9
Table 9
Claims
1. Utilisation de complexes alkoxyamine-boranes pour le stockage de l'hydrogène. 1. Use of alkoxyamine-borane complexes for the storage of hydrogen.
2. Utilisation selon la revendication 1, de complexes alkoxyamine-boranes pour le stockage de l'hydrogène suivi d'une étape de relargage de l'hydrogène. 2. Use according to claim 1, of alkoxyamine-borane complexes for the storage of hydrogen followed by a step of hydrogen salting out.
3. Utilisation de complexes alkoxyamine-boranes selon la revendication 1, les dits complexes alkoxyamine-boranes étant de formule (I), 3. Use of alkoxyamine-borane complexes according to claim 1, said alkoxyamine-borane complexes being of formula (I),
R NH (i) R NH (i)
BH3 BH 3
pour laquelle R et R' sont choisis parmi un hydrogène, un groupement alkyle ou cycloalkyle en Cl à C10. wherein R and R 'are selected from hydrogen, a C1 to C10 alkyl or cycloalkyl group.
4. Procédé de relargage d'hydrogène à partir de complexes alkoxyamine- comprenant une étape de déshydrogénation des dits complexes alkoxyamine-boranes. 4. Process for the release of hydrogen from alkoxyamine complexes comprising a step of dehydrogenation of said alkoxyamine-borane complexes.
5. Procédé de relargage d'hydrogène selon la revendication 4, comprenant une étape de mise en contact d'au moins un complexe alkoxyamine-borane avec un catalyseur ou une étape de chauffage thermique des susdits complexes alkoxyamine-boranes. 5. Hydrogen release process according to claim 4, comprising a step of contacting at least one alkoxyamine-borane complex with a catalyst or a thermal heating step of said alkoxyamine-borane complexes.
6. Procédé de relargage d'hydrogène selon la revendication 4, comprenant une étape de mise en contact d'au moins un complexe alkoxyamine-borane avec un catalyseur de rhodium, de platine, de palladium, d'or ou de nickel, notamment choisi parmi RhCl(PPh3)3, NiCl2(PPh3)2, Rh@TBAB et Ni@TBAB, Pd(OH)2/C, PtCl2, PdCl2, KAuC , Pt(PPh3)4 6. Process for the release of hydrogen according to claim 4, comprising a step of contacting at least one alkoxyamine-borane complex with a catalyst of rhodium, platinum, palladium, gold or nickel, in particular chosen from RhCl (PPh 3 ) 3 , NiCl 2 (PPh 3 ) 2 , Rh @ TBAB and Ni @ TBAB, Pd (OH) 2 / C, PtCl 2 , PdCl 2 , KAuC, Pt (PPh 3 ) 4
7. Procédé de relargage d'hydrogène selon la revendication 4, comprenant une étape de mise en contact d'un complexe alkoxyamine-borane avec RhCl(PPh3)3. 7. Process for the release of hydrogen according to claim 4, comprising a step of contacting an alkoxyamine-borane complex with RhCl (PPh 3 ) 3 .
8. Procédé de relargage d'hydrogène selon la revendication 4, comprenant une étape de mise en contact d'un complexe alkoxyamine-borane avec NiCl2(PPh3)2.
8. Hydrogen release process according to claim 4, comprising a step of contacting an alkoxyamine-borane complex with NiCl 2 (PPh 3 ) 2 .
9. Procédé de relargage d'hydrogène selon la revendication 4, comprenant une étape de mise en contact d'un complexe alkoxyamine-borane avec Rh@TBAB 9. Hydrogen release process according to claim 4, comprising a step of bringing an alkoxyamine-borane complex into contact with Rh @ TBAB.
10. Procédé de relargage d'hydrogène selon la revendication 4, comprenant une étape de mise en contact d'un complexe alkoxyamine-borane avec Ni@TBAB 10. Hydrogen release process according to claim 4, comprising a step of bringing an alkoxyamine-borane complex into contact with Ni @ TBAB.
1 1. Procédé de relargage d'hydrogène selon la revendication 4, comprenant une étape de chauffage thermique des susdits complexes alkoxyamine-boranes au-dessus de 80°C, préférentiellement au-dessus de 120°C. 1. The method for recovering hydrogen according to claim 4, comprising a step of thermal heating said alkoxyamine-borane complexes above 80 ° C, preferably above 120 ° C.
12. Procédé de préparation de complexes alkoxyamine-boranes de formule (I) comprenant une étape de mise en présence d'hydroxy lamines de formule (II), (II)12. Process for the preparation of alkoxyamine-borane complexes of formula (I), comprising a step of placing hydroxy lamines of formula (II), (II) in the presence of
pour laquelle R et R' sont choisis parmi un hydrogène ou un groupement alkyle en Ci à C10 ou cycloalkyle en C3 à C10, ou d'un de leurs sels, par exemple un chlorhydrate, avec NaBH4 et un acide minéral, préférentiellement H2S04 ou HCl, ce procédé ne nécessitant pas d'étape de purification. for which R and R 'are chosen from hydrogen, a C 1 -C 10 alkyl or C 3 -C 10 cycloalkyl group, or a salt thereof, for example a hydrochloride, with NaBH 4 and a mineral acid, preferentially H 2 SO 4 or HCl, this process not requiring a purification step.
13. Procédé de préparation selon la revendication 12, des complexes alkoxyamine-boranes suivants :
13. Preparation process according to claim 12, of the following alkoxyamine-borane complexes:
(1 ) (2) (3) (4) (5) comprenant une étape de mise en présence respectivement des chlorhydrates d'hydroxy lamines suivants :
avec NaBH4 et un acide minéral, préférentiellement H2S04 ou HCl, ce procédé ne nécessitant pas d'étape de purification.
(1) (2) (3) (4) (5) comprising a step of bringing into contact respectively the following hydrochloride hydroxylamine: with NaBH 4 and a mineral acid, preferentially H 2 SO 4 or HCl, this process not requiring a purification step.
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| Application Number | Priority Date | Filing Date | Title |
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| FR1758543A FR3070974A1 (en) | 2017-09-14 | 2017-09-14 | NEW PROCESS FOR STORING HYDROGEN |
| PCT/FR2018/052250 WO2019053382A1 (en) | 2017-09-14 | 2018-09-13 | New method for storing hydrogen |
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| US (1) | US20200255289A1 (en) |
| EP (1) | EP3681841A1 (en) |
| JP (1) | JP2020533265A (en) |
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| CN102173385B (en) * | 2011-01-21 | 2012-11-14 | 南开大学 | Method for synthesizing high-capacity solid hydrogen storage material ammonia borane by using amino complex |
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